Blocked isocyanates and isocyanated soybean oil as new chain extenders for unsaturated polyesters

Two different blocked isocyanates, diphenylmethane–bis‐4,4′‐ethyleneurea and diphenylmethane–bis‐4,4′‐carbamoil–ϵ‐caprolactam, and isocyanated soybean oil were used as chain extenders for low‐molecular‐weight unsaturated polyesters. Oligomeric polyesters (molecular weight = 600–700), taken from a manufacturing process in the sixth hour of a 16‐h polyesterification reaction, were reacted with these chain extenders, and the desired chain lengths (molecular weight = 1000–1500) were obtained in a very short time through the reaction of the chain extenders with the polyester end groups. The increase in the molecular weight was monitored with gel permeation chromatography. The obtained polymers were characterized with Fourier transform infrared and ¹H‐NMR and with styrene solubility and gel time measurements. After dilution with styrene, the polyesters were cured with a radical initiator. The thermal and mechanical properties of the cured polyesters were examined with dynamic mechanical analysis and thermogravimetric analysis tests and then compared to those of a commercially available reference unsaturated polyester. The results show that unsaturated polyesters can be chain‐extended with these compounds to shorten the polyesterification time substantially without alterations of the styrene solubility or gel time of the polyesters. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Lactic acid based poly(ester-urethane)s: The effects of different polymerization conditions on the polymer structure and properties

A two-step process for lactic acid polymerization is studied: in the first step the lactic acid is condensation-polymerized to a low-molecular-weight hydroxyl-terminated prepolymer; and then the molecular weight is raised by joining prepolymer chains together using diisocyanate as the chain extender. The resulting polymer is a thermoplastic poly(ester-urethane). In this study, we synthesized three different prepolymers and used three different diisocyanates as chain extenders. All of the prepolymers were hydroxyl-terminated, and their weight average molecular weights were 5,500 g/mol, 11,900 g/mol, and 26,000 g/mol. One of the diisocyanates was aliphatic, and the other two were stiff cycloaliphatic diisocyanates. The results indicate that of the tested diisocyanates, high weight average molecular weight can be achieved only by using aliphatic 1,6-hexamethylene diisocyanate. The cycloaliphatic diisocyanates produced poly(ester-urethane)s with weight average molecular weights which were quite low, but due to the stiffness of the polymer chains the glass transition temperatures can be as high as 60°C. The 1,6-hexamethylene diisocyanate (HDI) results also indicate that the molecular weight and network formation can be controlled independently by the amount of diisocyanate used and the polymerization conditions. Only the poly(ester-urethane)s which were produced with HDI had good mechanical properties, while the stiff diisocyanates produced very brittle polymers. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 865–873, 1997     

Chain extenders for polyester. II. Reactivities of carboxyl-addition-type chain extenders; bis cyclic-imino-ethers

The reaction behavior of such bis cyclic-imino-ethers as 2, 2′-bis(2-oxazoline), which had been proved in the previous paper to be an effective chain extender to couple carboxyl terminals of linear polyesters through addition reaction, has been studied to evaluate their practical applicability as the chain extenders for poly(ethylene terephthalate) and poly(butylene terephthalate). It has been observed that a wide range of excess use of 2,2′-bis(2-oxazoline) resulted in polyesters of almost similar molecular weight. In addition, when excess amounts of the chain extender were added and the reaction conditions were fixed, the ratio of the coupled carboxyl terminals to the initial carboxyl terminals became constant regardless of the initial molecular weight and carboxyl content (CV). The results indicate that the chain-extended polyesters possess predetermined molecular weight and CV, both of which depend only on the molecular weight and CV of the initial polymers, and not on the amount of the chain extender added.     

Reactive polymers in diagnostics: Syntheses and characterizations of nucleic acid probes and maleic anhydride-co-methyl vinyl ether polymers

Maleic anhydride-co-methyl vinyl ether copolymers were used as reactive polymers to link oligodeoxyribonucleotides (ODN) to make oligonucleotide-copolymer conjugates of potential applications in diagnostics. The anhydride moieties of the copolymers were used for the covalent binding, via the formation of a peptide bond, on reaction with DNA probes that were amino modified at the 5′ position. The best coupling yields were obtained by carrying out the reaction in a DMSO-borate buffer (95/5 volume ratio) mixture at high ionic strength. Copolymers and ODN-copolymer conjugates were characterized by size exclusion chromatography and multiangle laser light scattering detection. The average molecular weights of the formed conjugates were relatively high, in the 10⁶ g/mol range, resulting from the crosslinking of several copolymer molecules during coupling. Coupling DNA probes onto smaller molecular weight polymers did not result in the formation of very high molecular weight conjugates showing that copolymer chain interpenetration was a determining factor of the crosslinking process that occurs during the coupling reaction. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2567–2577, 1997     

尼龙6化学扩链

用挤出机熔融共混法,以双２口恶唑啉和双酰基双内酰胺化合物为扩链剂,对ＰＡ６进行化学扩链,使ＰＡ６的分子量由１６．７ｋｇ／ｍｏｌ提高到２１．０ｋｇ／ｍｏｌ,偶联效率最高可达７０％;同时考查了扩链剂用量、铜盐、共混温度与时间以及后热处理对扩链效果的影响。     

Preparation and characterization of high‐molecular‐weight poly(l‐lactic acid) by chain‐extending reaction with phosphites

Poly(l ‐lactic acid) (PLLA) of high molecular weight was prepared by a chain‐extending reaction in a microcompounder. Phosphites were used as chain extenders to increase the molecular weight of the PLLA prepolymer, which was prepared by the bulk polycondensation of l‐lactic acid. The effects of the amount of phosphite, the temperature, and the screw speed on the torque of the PLLA melt were studied. Under the optimal conditions, the molecular weight of PLLA increased from 62,100 to 126,000 g/mol. The chemical structure and crystallinity of PLLA were characterized by Fourier transform infrared spectroscopy, ¹H‐NMR and ¹³C‐NMR, differential scanning calorimetry, and X‐ray diffraction. The mechanical properties of PLLA were measured. The results indicate that triphenyl phosphite (TPPi) was an effective chain extender for PLLA. The role of the TPPi in chain extending is suggested to be an esterification‐promotion agent. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Chain extension reactions of unsaturated polyesters with bis(2‐oxazoline)s

Two different bisoxazolines, 2,2′‐(1,3‐phenylene) bis(2‐oxazoline) (1,3‐PBO) and 2,2′‐bis(2‐oxazoline) (BO) were investigated as chain extenders for short chain unsaturated polyesters (UPEs). These extenders reacted readily with carboxyl ends of unsaturated polyesters, leading to rapid molecular weight increase through coupling of oligomeric chains. Commercially available unsaturated polyesters commonly have molecular weights around 1500, usually reached after a 20‐h polyesterification reaction. When bisoxazolines were reacted with short UPE chains obtained at the 6th hour of a commercial polyesterification reaction, the molecular weight of UPE reached 1500 within 5–30 min, which provides economies and prevents the glycol loss and yellowing which are associated with extended reaction times. Styrene solubility, gel time, and thermal and mechanical properties of the chain extended polyesters remained comparable to the commercial UPE, with 8–10 min of gel time and a storage modulus about 3000 MPa. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Toughened poly(butylene terephthalate)s and blends prepared by simultaneous chain extension,interfacial coupling,and dynamic vulcanization using oxazoline intermediates

Toughness of poly(butylene terephthalate) (PBT) was improved by reactive blending of PBT with 2-substituted 1,3-oxazoline intermediates such as low-molecular-weight bisoxazolines, and oxazoline-functionalized nitrile rubbers derived from both nitrile liquid rubber (Nipol®) and high-molecular-weight hydrogenated nitrile rubber (Therban®). Conversion of 7 mol % of the nitrile groups of Nipol into 1,3-oxazoline, corresponding to less than 1 oxazoline group per chain, was sufficient to afford melt strengthening and substantially improved dispersion and interfacial adhesion of the nitrile rubber microphases in the PBT continuous phase. Also in the case of high molecular weight Therban, oxazoline functionalization significantly improved compatibility with PBT. Best results in terms of toughness/stiffness balance, with impact strength exceeding 200 kJ/m², was achieved when PBT was blended with both oxazoline-functionalized high-molecular-weight hydrogenated nitrile rubber and low-molecular-weight bisoxazoline chain extenders. The outstanding performance of such PBT blends, containing 10 and 20 wt % oxazoline-modified Therban and 0.6–1.1 wt % bisoxaoline chain extender, respectively, was attributed to simultaneous bisoxazoline-mediated PBT chain extension, interfacial coupling and dynamic vulcanization of the oxazoline-functionalized nitrile rubber. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 633–642, 1997     

Chain extending of lactic acid oligomers. 2. Increase of molecular weight with 1,6-hexamethylene diisocyanate and 2,2′-bis(2-oxazoline)

Lactic acid polymers were synthesised from oligomers by the addition of highly reactive 1,6-hexamethylene diisocyanate (HMDI) and 2,2′-bis(2-oxazoline) (BOX) as chain extenders. The effects were studied of adding the extenders simultaneously and sequentially and in different amounts. The reactions were followed and the polymers obtained were structurally characterised by size exclusion chromatography and spectroscopy (NMR and FTIR). High molecular weight poly(lactic acids) were obtained by both simultaneous and sequential addition. The mode of addition and the amounts of extenders had a considerable effect on the branching. The addition of HMDI before BOX in the sequential linking produced more highly branched polymers than did the simultaneous addition. Branching and crosslinking reactions were identified as side reactions of the chain extending reactions. The gel formation was attributed to the reactions of BOX and HMDI with urethane and amide but not with oxamide.     

Impact of the chain extension of poly(ethylene terephthalate) with 1,3‐phenylene‐bis‐oxazoline and N,N′‐carbonylbiscaprolactam by reactive extrusion on its properties

In this article, the material properties of chain extended poly(ethylene terephthalate) (PET) by application of the chain extenders, 1,3‐phenylene‐bis‐oxazoline (1,3‐PBO), N,N′‐carbonylbiscaprolactam (CBC), and combinations thereof are investigated aiming at an application during fiber production from postconsumer PET. The chain extension is performed in one step by a reactive extrusion process. The chain extenders are linearly linked to the COOH and/or OH terminal groups of PET. The influence of the chain extension on the properties of PET is analyzed by measurement of the inherent viscosity, size exclusion chromatography, and carboxyl end‐group titration. Furthermore, the impact of the chain extension on the thermal and rheological properties of PET is studied in detail by differential scanning calorimetry and rheology. The results demonstrate that chain extenders have impact on the properties of PET in dependence on their chemical composition and concentration. The improvement of the molecular weight of the obtained compounds is achieved in an effective and economical approach by the addition of small concentrations of chain extenders (0.2 wt% 1,3‐PBO or 0.3 wt% CBC) without significant negative impact on the properties of PET. POLYM. ENG. SCI., 59:284–294, 2019. © 2018 Society of Plastics Engineers     

Polyurethane elastomers with amide chain extenders of uniform length

Toluene diisocyanate based polyurethanes with amide extenders were synthesized poly(propylene oxide) with a number average molecular weight of 2000 and endcapped with toluene diisocyanate was used as the polyether segment. The chain extenders were based on poly(hexamethylene terephthalamide): hexamethylene diamine, bisamine-diamide and bisamine-tetra-amide. The linear poly(ether bisurethane-bisurea-amide)s (PUA) were colorless transparent thermoplastic elastomers with a high molecular weight. The polymers were analyzed by IR and DSC, the morphology studied by TEM, the mechanical properties studied by DMTA and the tensile, the elastic properties by compression and tensile set and thermal stability by melt rheology.The phase separation with these amide extenders was by crystallization. Increasing the length of the amide chain extender increased the modulus and the melting temperature of the PUA without changing the good low temperature properties. Also the elastic properties improved with amide segment length. The fracture stress increases with amide extender length. At 200 °C, the melt stability of the PUA with the bisamine-diamide chain extender was good.     

Effect of Two‐Step Chain Extension using Joncryl and PMDA on the Rheological Properties of Poly (lactic acid)

This research considers a two‐step chain extension reaction in the presence of two chain extenders, Joncryl and Pyromellitic dianhydride (PMDA), as a solution for poor melt properties of poly (lactic acid) (PLA). The aim of adding PMDA is to increase the carboxyl groups via the anhydride ring‐opening reaction so that the reaction between PLA and Joncryl could be facilitated since the reactivity between the epoxy and carboxyl group is more than epoxy and hydroxyl group. The reactions are confirmed by measuring the acid value, and a two‐step reaction mechanism is suggested. Shear and elongational rheological properties of the samples are investigated; furthermore, gel permeation chromatography analyses and tensile tests are exploited for studying the molecular weight and tensile properties, respectively. The results show that the chain extension reactions lead to an increase in the storage modulus, complex viscosity, and molecular weight. Also, the PLA chains which are extended utilizing both chain extenders simultaneously evince a synergistic improvement in the shear and elongational rheological properties due to longer segments between branching points on the structure.     

Chain extenders for polyesters. V. Reactivities of hydroxyl-addition-type chain extender; 2,2′-bis(4h-3,1-benzoxazin-4-one)

In our previous study,¹ 2,2′-bis(4H-3,1-benzoxazin-4-one) (BNZ) was found to be most effective among the tested chain extenders in coupling hydroxyl terminals of linear polyesters through addition reaction. Detailed studies on BNZ chemistry have been made using poly(ethylene terephthalate) and poly(butylene terephthalate) as the polyester. It has been observed that use of BNZ, equivalent amount to the hydroxyl terminals of the initial polymer, resulted in the highest molecular weight. In contrast with the case of 2,2′-bis(2-oxazoline), which was found to be the most effective carboxyl-addition type chain extender and a wide range of its excess use was allowed,^2,3 an excessive use of BNZ resulted in lower molecular weight polymer. Thus, when an equivalent amount of BNZ to the hydroxyl terminals was used, the molecular weight of the resulting polymer could be determined by the carboxyl content of the initial polymer, regardless of its initial molecular weight.     

Radical polymerization of acrylamide initiated by ceric ammonium nitrate-methionine redox initiator system

The polymerization of acrylamide, initiated by a cerium (IV) [Ce(IV)] ammonium nitrate-methionine redox initiator system, was carried out in an aqueous solution at different reaction conditions. The dependence of molecular weight and polymerization yield on the concentration of Ce(IV), polymerization time, and temperature was determined. The molecular weight distributions (MWD) of the resulting polymers were examined using the HPLC method. Based on the HPLC results, optimum reaction conditions were determined that provided an opportunity to obtain a polymer that had a narrow MWD. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1643–1648, 1997     

Chain extension of recycled PA6

Recycling of polymers is a necessity in our intensively consuming polymer world but the nature of polymers is such that they are prone to thermal degradation when re‐extruded and this poses technical challenges to recycling. This article describes research that seeks to rebuild the structure of degraded PA6. We present data from controlled experiments with pristine pPA6 extruded to form a base recycle rPA6 to which we added two chain extenders, separately: one with anhydride multifunctionality (ANHY), highly reactive with amide groups and one with epoxy multifunctionality (EPOX), less reactive. We found from rheological data carried out in the linear viscoelastic region (so as to study structural changes) a striking difference in the ability of the chain extenders to rebuild structure: 306% increase in the complex viscosity of rPA6/ANHY compared to 25% in that of rPA6/EPOX of the base rPA6. Mechanical and thermal (DSC and TGA) tests confirmed the superior efficacy of the multifunctional anhydride chain extender. Beside the practical benefit that ensues from this research, it also provides a strategic platform to develop chain extenders for other degrading polymers on the basis of understanding the degradation chemical reaction and targeting the most reactive end group of the split chains. POLYM. ENG. SCI., 58:1037–1042, 2018. © 2017 Society of Plastics Engineers     

Synthesis,thermal, and mechanical characterization of liquid-crystalline polyhydroxyethers

High molecular weight liquid-crystalline polyhydroxyethers, containing functional hydroxy groups, were synthesized from an aromatic diol and the diglycidylether of an aromatic diol. The polymers showed a liquid-crystalline melt when about 70% or more of the aromatic units in the chain were biphenyl units. Tensile modulus values varied from 3 GPa for as-cast films to 6 GPa for drawn films. These polymers are potentially suitable candidates to reinforce common thermoplastics by reactive blending. For this purpose polyhydroxyethers have been prepared, having a liquid-crystalline melt in the processing range of PET, viz. 260–290°C. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1971–1978, 1997     

新型水性聚氨酯缔合型增稠剂的制备与表征

利用六亚甲基二异氰酸酯(HDI)与聚乙二醇(PEG)合成预聚体,加入系列扩链剂进行扩链,并通过十六醇封端合成了水性聚氨酯缔合型增稠剂(HEUR)。采用傅里叶变换红外光谱仪表征了HEUR的结构,通过粘度的测定,研究了不同扩链剂对HEUR增稠性能的影响,并对HEUR相对分子质量大小及分布系数进行测定。结果表明,1,4-丁二醇作为扩链剂合成的HEUR,其增稠性能以及纯度要好于1,2-十四碳二醇、1,2-辛二醇、一缩二乙二醇扩链剂合成的HEUR。     

Fabrication and Properties of Modified Poly(butylene terephthalate) with Two-Step Chain Extension

High-viscosity, low-crosslinked poly(butylene terephthalate) (PBT) from organic chain extenders and inorganic particles are prepared. PBT modification adopted from multifunctional, commercially available chain extension containing nine epoxy groups (ADR9) occurs in the first-step chain extension; hydroxyl addition modified dioxazoline (BOZ) serves as the second step. Anion stratiform inorganic hydrotalcite (HT) is used to adjust the crystallization behavior and damp-heat aging properties of PBT. The reaction between the chain extender and PBT end-groups such as carboxyl (–COOH) and hydroxyl (–OH) enhances the interfacial bonding between the PBT matrix and dispersed HT phases. With a fraction of chain extenders in the PBT matrix, the chain-extended PBT exhibits higher mechanical properties, intrinsic viscosity, average molecular weight, and melt viscosity than those of unmodified PBT. Damp-heat aging resistance measurements show correlation with initial carboxyl content in the resin. Reducing the concentration of carboxyl end-groups in the resin is shown to increase hydrolytic stability. The modified PBT resin can be used in optical fiber communication cable industry for its high level of damp-heat aging resistance as well as good mechanic properties.     

Synthesis of linear polymers containing benzoxazine moieties in the main chain with high molecular design versatility via click reaction

Linear polymers with benzoxazine rings in the main chain have been synthesized applying click chemistry approach. These polymers possess molecular weights significantly higher than the benzoxazine polymers which have been chain extended via Mannich reaction. The number average molecular weight is estimated from size exclusion chromatography (SEC) to be between 20,000 and 40,000 Da. The structure of the polymers is confirmed by ¹H and ¹³C nuclear magnetic resonance spectroscopy (NMR) and Fourier transform infrared spectroscopy (FTIR). Differential scanning calorimetry (DSC) is used to study crosslinking behavior of the polymers. The nature of the low temperature exotherm DSC peak observed in this work and the previous work of other authors is studied by model reactions. It is due to thermal coupling of the residual propargyl and azide end groups in the absence of active catalyst. In addition, a novel diazide-functional benzoxazine monomer has been prepared, showing a tremendous flexibility for applying click reaction to obtain various polymer architectures. Three types of polymers have been prepared from dipropargyl- and diazide-functional benzoxazine monomers. These polymers have been characterized by dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA).